Ethers of endoethylene-substituted cyclopentanols



Patented Nov. 26, 1946 ETHERS 0F ENDOETHYLENE-SUBSTITUTED CYCLOPENTANOLSHerman A. Bruson, Philadelphia, Pa., assignor to I The Resinous Products& Chemical Company, Philadelphia, Pa., a corporation of DelawareNo'Drawing. Application May 24, 1944, Serial No. 537,183

8 Claims. (Cl. 260-611) This invention relates to addition-rearrangementproducts from organic compounds having alcoholic hydroxyl groups andadductsof cyclopentadiene with mono-olefinic compounds having at leastthree carbon atoms, said products being ethers of anendoethylene-substituted cyclopentanol.

In my copending application, Serial No. 476,- 640, filed February 20,1943, it is shown that nonresinous polycyclopentadienes having twodouble bonds per molecule, such as dicyclopentadiene,tricyclopentadiene, and tetracyclopentadiene add alcohols in thepresence of acidic condensing agents toform addition-rearrangementproducts which ar ethers of a new ring system termed thenordicyclopentadiene ring system.

In accordance with the present invention, which is acontinuation-in-part of copending application Serial No. 529,195, filedApril 1, 1944, adducts of cyclopentadiene with mono-olefinic compoundshaving at least three carbon atoms in the molecule are reacted withalcohols in the presence of acidic condensing agents to form additionproducts which are, rearranged ethers from endo-ethylene-substitutedcyclopentanols. A typical illustration is that, for example, involvingthe action of an alcohol, ROH, upon the cyclopentadiene-styrene adduct.

The product formed by the molecular additionrearrangement'is veryprobably that represented by formula (A). In any event, the product'is'not a. simple addition of (R -O) to one side of the double bond andof H to the other. The reaction involves both addition and rearrangementand leads to a new class of substituted cycllc com-- pounds which arenot available by any previously proposed method of synthesis.

Various adducts of cyclopentadiene with monoolefinic compounds havingthree or more carbon allyl alcohol, allyl chlorlde,;allyl benzoate,allylacetate, allyl oleate, vinyl methyl" ketone, vinyl' acetate, vinylvbenzoate, and the like. There may also be used other adducts ofcyclopentadiene with olefinic compounds, such as coumarone, sairole,eugenol, and with allyl ethers, such as benzyl allyl ether, phenyl allylether, octyl allyl ether, and the like.

In practicing this invention, it has been found that a wide variety oforganic compounds containing one or more alcoholic hydroxyl groups maybe employed. The hydroxyl group is preferably primary or secondary.Compounds containing a tertiary hydroxyl group may also be used,provided, however, that they are not readily dehydrated.

The useful alcoholic hydroxyl-containing compounds may be aliphatic,arylaliphatic, cycloaliphatic, hydroaromatic, or heterocyclic and may besaturated or unsaturated, straightor branched-chained, or cyclic. It hasalso been established that the non-hydroxyl portion of the reactinghydroxyl-containing compound may contain a wide variety of groups orsubstituents, for example, halogen, cyano, thiocyano', nitro, keto oracyl, mercapto, ether, acylox'y, alkoxy, aryloxy. carbalkoxy, or carboxygroups, etc.

It should be noted at'this point that,-in the case of alcoholichydroxyl-containing compounds having free carboxyl groups. excesscyclopentadiene-oleflne adduct is necessary since esterlfication of thecarboxyl group byaddition and simultaneous rearran ement occurs inaddition 'to etheriflcation with the alcoholic hydroxyl group.

From the 'above discussion, it will be evident that under the influenceof acidic condensing agents' cyclopentadiene-olefine adducts of the typeset forth formv rearran ed ethers with a wide variety of alcoholichydroxyl-containing "compoundsand' that'the reaction is onelof wideapplicability. Hydroxyl-containing reactants. of

perhaps greatest interest belong tofthe-g'eneral class of iunsubstitutedalcohols, whether monohvdric or-'-polyhydric,..which aren'ot dehydratedpat 60fC.1by-sulf uric acid. JThere are, however, important types ofreactantsother than the simple alcohols. Other important groups includehydr'oxy-acid esters. ,hydroxy acids, hy'droxy-ketones.hydroxy-lactone's, *hydroxy-aldehydes,

ether alcohols, c'yano alcohols. thiocyano alco-v hols. halohydrins,nitro: alcohols, andfp'olymeric hydroxylecontaining compounds, including polyvinyl alcohol. polysaccharides, starches, sugars,

cellulose, cellulose e'thers', cellulose esters,;and the p 9' like.

55 r gl atg useful hydroxyl-containing corn col-1,3, diethylene glycol,

propanol, isoethoxyethanol, butoxyethanol, phenoxyethanol,

ethylene glycol, propylene glycol, butylene' glytriethylene glycol,polyethylene glycols, di-isopropylene glycol, diethylene glycolmonoethyl ether, 'diethylene glycol monobutylether, diethylene glycolmonophenylether, glycerol, glycerol monochlorohydrin, glyceroldichlorohydrin, glyceryl-a-phenyl ether, 2 ethyl hexandiol 1,3, glycerylafldimethyl ether, trimethylene glycol, tetramethylene glycol,decamethylene glycol-1,10, pentaerythritol, ethylene/chlorohydrin,propylene chlorohydrin, ethylene bromohydrin, propargyl alcohol,ethylene cyanohydrin, p thiocyanophenoxy ethanol,2-nitro-2-methyl-1-propanol, p thiocyanoethoxyethanol, ptertiary-butylphenoxyethanol, 0 cyclohexylphenoxyethanol,2,4-dichlorophenoxyethanol, p ter octylphenoxy ethanol, pphenylphenoxyethanol, p-naphthox'y ethanol, 2 nitrophenoxyethanol, pacetylphenoxyethanol, p-benzoylphenoxyethanol, cyclohexanol, 0-, m-, orp-methylcyclohexanol, cyclopentanol, 0- or p-cyclohexyl-cyclohexanol,p-tertamylcyclohexanol, hydroxydihydronordicyclo- -entadiene, borneol,fenchol, cholesterol, ethyl glycolate, ethyl lactate, dimethyl tartrate,ethyl citrate, benzyl alcohol, 2 nitro'2-methyl-l,3- propanediol,ethyl-IO-hydroxy-stearate, tetrahydrofurfuryl alcohol, phenylthioethanol, ceryl alcohol, 2-nitro-2-ethyl-1,3-propanediol, castor oil,hydrogenated castor oil, ethyl ricinoleate, ethyl maleate, sorbitol,dibutyl tartrate, glycerylapy-diphenyl ether, mannitol, ethylene glycolmonobenzylether, and many others. The hydroxyl-containin compound neednot be pure. There may be used, for instance, technical alcoholmixturessuch as are obtained as by-products from the syntheticproduction of methanol by the reaction f hydrogen and carbon monoxideand known as higher alcohols from the methanol synthesis. These comprisebranchedchained primary and secondary-alcohols having from about 7 toabout 18 carbon atoms and in .some cases even more.

Mixtures of higher aliphatic alcohols obtained by the catalytichydrogenolysis of fatty glycerides or of higher fatty acid esters maylikewise be used.

Among the acidic condensing agents or catalysts which serve to promotethe addition-rearrangement of alcoholic hydroxyl-containing compoundswith cyclopentadiene mono-olefines of the type set forth are borontrifluoride and its coordination complexes with oxygenated compounds,such as ethers, as, for example, BF'mCaH'iOC3H'1; carboxylic acids, as

aatzcmooon carboxylic esters, as BFaCH'sCOOCzHs; ketones, such asBF3.CH3COCH3; alcohols, such as BF 5.2C4H9OH; and water, such asBFs.(H2O)= where :c is one or two. There may also be used as a catalystsulfuric acid, its esters, such as ethyl acid sulfate, aromatic'sulfonic acids, such as 4 toluene sulfonic acid, or aliphatic sulfonicacids, as butylsulfonic acid and the like.

Sulfuric acid is of particular value in promot-- ing reactions involvingthe lower primary aliphatic alcohols. It is generally of use in the caseof other alcohols also, which are not readily polymerized/or dehydratedby the presence of concentrated sulfuric acid.

The boron trifiuoride group of catalysts is one of considerable value.of these, the complexes with ethers are of particular utility since theyare soluble in the reaction mixtures and produce no troublesomeby-products. Typical of these complexes are BFB.C:H9OC:H5 andBF3.C4H9OC4H9, with diethyl ether and din-butyl ether, respectively.

The quantity of active catalyst employed may be varied over a widerange. Good results have been obtained with as little as two per cent ofcatalyst, based on the weight of the cyclopentadiene adduct, up to andexceeding a molar equivalent of the catalyst per mol of adduct used. Thecatalysts need not be used under anhydrous conditions. In fact, thepresence of water in small amounts often increases the rate of reaction.

The addition-rearrangement reaction involving an alcoholichydroxyl-containing compound and the adduct of cyclopentadiene and amono oleflniccompound is readily carried out in the.

presence of one or more acidic condensing agents. The reaction may beinitiated bymixing the components and catalyst at room temperature,

at temperatures even around 0 C. in some cases,

or at elevated temperatures. While it is generally desirable to controlthe temperature at the start, the reaction may be carried to completioneither by continuing the reaction for a long time or by raising thetemperature to accelerate the reactions involved. Temperatures as highas 100 C. to about 200 C; may thus be used. The reaction range of about50 to 125C. is, however, generally the most useful and is to bepreferred.

In some cases the reactions are sufllciently exothermic that it isdesirable to cool the reacting mixture in order to control the reaction.This may also be controlled by the rate of mixing the. reactants and bythe use of a solvent or diluent such as ethylene dichloride or dioxane.

After the'reaction' has been carried to a de-' sired point,- the acidiccondensing agent is removed, as by washing with water or byneutralization. The reaction product may then be distilled in manycases, or otherwise purified, as by treatment with decolorizing clay orcarbon, stripping, extraction, etc.

The following examples illustrate this invention, it being understoodthat the proportions, temperatures and time can be varied to aconsiderable extent without departing from the spirit of the invention.

For the purpose of this invention it is desirable, although notnecessary, to employ not more than one mol equivalent of the alcohol permol of the adduct.

Example -1 A mixture of 4 g. of BF:.O(C4I-Ia)a 108 g. of

ethylene chlorohydrinand 134 g. of the cyclopentadiene-ally1 phenylether adduct distilled over at 160 -170 (1/1 mm. a. a col 1}- wasstirred at 95 C. for six hours. The product was washed with dilutesodium hydroxide solution, then ,with water, dried, and distilled invacuo to yield 138 g. of the p-chloroethoxy endoethylene phenoxymethylcyclopentane as a colorless oil boiling at 166-169 C./1 mm. having theprobable formula v ,H' C i The cyclopentadiene-allyl phenyl ether adductused is a colorless oil boiling at 134 C./6 mm.

obtainable by heating cyclopentadiene or dicyclopentadiene with allylphenyl ether at 1'70-180 C. as described in copending application SerialNo. 529,196, filed April 1, 1944.

Example 2 A mixture of 9.6 g. of methanol, 2 g. 01.95% sulfuric acid,and 1'7 g. of the cyclopentadienev styrene adduct distilled over at135-148 C./10 mm. as a color-' less oil. Upon redistillation the purecompound boiled at 14;0f ,-145 (IL/10 mm.

Example 3 A mixture of 16 g. of ethylene-chlorohydrin,

1 g. of BF3.0 (C4H9)2, and 17 g. of 2,5-endomethylene 1,2,5,6tetrahydrodlphenyl stirred at 959-97 C. for four hours. The prodduct waswashed with sodium carbonate solution and water, dried, and distilled invacuo.

The p-chloroethyl ether of phenyl endoethylene cyclopentanol having theprobable formula Ca i... l. l I g Q cicmc'm-o- 11-, 0

less oil. Upon redistillation the pure compound boiled at 148-152C./0.5-1 mm.

Example 4 i A mixture of 31 g. of ethylene glycol (0.5 mol). 2 8. 0fBF3.0(C4H9) 2, and 31 3. 0f 2,5-endomethylene-1,%5,6-tetrahydrodiphenylwas stirred was i at 95 -9'l C. for seven hours. The product was washedwith sodium hydroxide solution and with water, then dried, and"distilled in vacuo. The

p-hydroxyethyl ether of phenyl endoethylene 5 cyclopentanol having theprobable formula CHI CgL CH1 1H1 Ho-cmcm-o- 11 distilled over at 160-163C./2 mm. as a color- 15 the pure compound boiled at 153 163 C./1 mm.

Example 5 A mixture of 11.6 g. of allyl alcohol, 1 g. of BFa.O(C2I-I5)z, and 17 g. of 2,5-endomethylene- 1,2,5',6-tetrahydro-diphenyl washeated at 90 C.

20 for four hours. The product was worked up as cyclopentane havingthe*probable formula distilled over at 1551'l0 C./10 mm. as a'colorlessoil. Upon redistillation the pure compound boiled at 164-168- C./10 mm.

Example 6 A mixture of 3g. of nraowlmn, 64 g. of

' ethylene chlorohydrin and 90 g. of cyclopentadiene-allylbenzoateadductwas stirred at 97 C. for eight hours. The product was washedwithdilute soda solution, then with water, dried, and distilled in vacuo toyield 96 g. of the ,B-chloroethoxy derivative as a viscous oil boilingat 195-200 C./1-2 mm. having the probable formula Example 7 A mixture of11.9 g. of 2-nitro-2-methyl-1- propanol, 0.5 g. of BR.O(C2H5) 2, and 1'1g. of 2,5-endomethylene 1,2L5,6' tetrahydrodiphenyl was stirred at 90 C.for three hours. The product was washed with water, dried, and'distilledin vacuo.

The nitro-isobutyloxy-phenyl endoethylene cyclopentane having theprobable formula CH Cgl CH| Y on, i H, CHa-J)CH20 H-l- O l lo: (a boiledat 180-183 C./11 mm. It was a pale yellow oil.

I Example 8 A mixture of 17' g." of 2,5-endomethylene-1,2,5,6-tetrahydrodiphenyl, 14.7 g. of p-thiocyanoethoxyethanol, and 3g. of BF3.O(C4H9)2 was stirred at 95 C. for seven hours. The product waswashed with dilute soda solution and water,

"Z less oil in a yield 01' '17 gr Upon redistillation;

in Example 3. The allyloxy phenyl endothylene" there was added 4' autismin vacuo. The thiocyanoethoiwthen ethoxy-phenyl endoethylene'cyclopentane havinsthe probable formula C(sl OHs its on cg on H2: HaCEiro-om-ln. l H 23H}; was stirred at 95 e. for six hours. The productwas washed with dilute sodium hydroxide solution, then with water,dried, and distilled in vacuo to yield 180 e.- oi the p-chloroethoxyderivative as a colorless oil boiling at 185-195 (L/0.54 mm. havingtheprobable formula CH O l OH| s. a H-O-CHsCHsCl m r t H i The cyclopentadiene p-tertiary butylphenyl allyl ether ad uct used above in: cyclopeztadiene or dicyclopent'adiene with ptertiary buylphenyl allyl ether at170- 175 0.

Example To a, mixture of 80.5 g. of ethylene chlorohydrin and 88.5 s. orpropionitrile adduct s. of momma: and the mixture stirred at 95-97 C.for seven hours.

is a low melting solid boiling a 140 C./i mm. obtained by heat- 'ter andwith dilute and 2 a. or Brim was stirred for six hours. The product waswashed at 95 C.

with wa- A soda solution and then distilled in vacuo.

The ether ester having the probable formula GE cm Hal om-on-o-miz OOCaHs4 distilled over at l60=-l70 Q/LM min: asacolcyclopentadiene-p-allyloxy- The product was washed with dilutesodium hydroxide solution, then with water, dried, and

distilled in vacuo.

The p-chloroethoxy derivative obtained boiled 'at 184-169".C./1 mm. Itwas a colorless thick oil, having the probable formula ca m.

-OHr-OCH:OH|ON' l The yield amounted to '14 y Example 11 A mixture of asg. of ethyl lactateyi'z g. of 3.5-endom ethylene-1,2,5,8 tetralwdrodiphenyi C. for four hours and orless oil.

Essa/awe 22 A mixture or s so of ammcimur ass a. dc ethylene chlorohy,pentadiene-allyiowethanol adduct was stirred at 95 c. ior eight hours.The prod-.

uct was washed with dilutesodium hydroxide solution, then with water,dried, and distilled 'in vacuo to yield 89 g. of the p -chloroethoxyderivative as a colorless oil boiling at 162-'185 C./0.5-1 mm. havingthe probable f f ula on t' oi om clcmom-o- 11-1? capo-(nudismH Example13 A mixture oi 24.9 s. ot'p-chloroethoxyethanol, 17 g; of2.5-endomethylene-1,2,5.6-tetrahydrodiphenyl, and 1 g. 01.315.0(04Hs):was stirred at worked upby washing with soda solution and with water,followed by vacuum distillation.-

The product having the probable formula.

1 d 1 olomom-o-omom-onil-Z O distilledover at mot-1st lessviscous oil.

c. 1. s mm. as a 0010!- Example 14.

A mixture or 22 g. of glyceryl--monochlorohydrin, 17 g. of2,5-endomethylene-i,2,5,6-tetrahydro-diphenyl. and 1 g. of B1'5.O(C4Ha)=was stirred at 90-95 y then cooled, washed with dilute sodium hydroxidesolution and water, and distilled in vacuo. The product having theprobable formula olonscrjron-onro ln+ O boiled at ism- 0. mm. It is athick oil.

E's-ample 15 A mixture of 35.4 g. of n butoxyethanol cm.

and 158 g. of the cycle C. for tour and one-half hours tyl Ceilosolve),1'! g. or 2,5-endomethylenea colorless oil boiling at 130-135 C./1 mm.ob-

l,2,5,6-tetrahydro-diphenyl, and 3 g. of tained by heatingcyclopentadiene or dicyclopen- B175 oa tadiene with sairole at PUP-180C. g was stirred at 95- 9'l C. for seven hours. The Example 18 productwas washed with dilute sodium hydrox- A mixture of 6 g. o!BF'a.O(C4H9)2, 160 g. or

ide solution, then with water, and distilled in ethylene chlorohydrin,and 148 g. of cyclopenvacuo. The n-but'oxyethoxy endoethylene phenyltadiene-vinyl acetate adduct cyclopentane having the probable formula Ion I 0 c l cm r 1 was stirred at 95 C. for five and one-half hours. o aThe product was cooled washed with dilute soda 1 1, c l 1 gi l l l' l iy?sld li gra s 5 mm as a o ess SOIlltIOIL'thGII with water, dried, anddistilled in 4 vacuo to yield 85 g. of the rearranged ether as a Example16' colorless oil boiling at 108-115 C./1 mm. having A mixture of 10.6g. of diethylene glycol, 34 g. I the P bab e formula: of2,5-endomethylene-1,2,5,6-tetrahydro-diphenyL-and 3 g. of B .O(C4H9)2was stirred for seven of, hours at 8590 C. and worked up as in Exam- HIple 15. Two products were obtained. One product was -q9,.cm

a colorlessoil boiling at 200-210 C. at 12 mm. M c having the probableformula E m l 19 CH A mixture r 5 gjer'BFrowrHm, 36 g. of g 3o ethylenecyanohydrin, and 55 g. or cyclopenta- -diene-indene adduct l I OH onHO-cmom-o-cmcmon-l O {L\ A a H; The other product was a thick oilboiling at 285- n n n 290 C./1.5 mm. having the probable formula 1 v fion I on v c gjjcm l l on,

H2 2 This example illustrates the factthat in the was stirred at 95 C.for four hours. The product case of polyhydric alcohols one or more ofthe was washed with water, dried, and distilled in alcoholic hydroxylgroups may be reacted to vacuo to yield g. of the rearranged cyanoethylgive one or more ether linkages to an endoethylether as a colorless oilboiling at l'74-1'l6 C./2 ene cyclopentane ring system. mm. having theprobable formula 0 011 CH Example Y Y A mixture of 5 g. of BFa.O(C4H9)2,101 g. of C CH ethylene chlorohydrin, and 158 g. of the cyclo- Ipentadiene-safrole adduct H v {-on r w v v h, cfi 0 1pm o v Example 20 HL I 1 A mixture of 10 g. or BFa.O(C4H9)2, 92 g. o c1! 13-43 -0 glycerol,and 55 g. of cyclopentadiene-indene ad- (so duct was stirred at -95 C.for eight hours.

A The product was washed with dilute sodium hydroxide solution, thenwith water, dried, and distilled in vacuo to yield 42 g. oftherearranged glyceryl mono-ether as a colorless oil boiling at 6;] 200C./0.5 mm. having the probable formula was stirred at 95 C. for eightand one-half hours. The product was washed with dilute potassiumhydroxide solution, then with water, dried, and distilled in vacuo toyield g. of the p-chloroethoxy derivative as a pale yellow oil boilingat 190 c./1-2 mm. having the probable forv CH E mula cg \CH-C/ cn a L Ic 70 HOCHr-CHOH-CHr-O- n--- H i 112 L of, 0Q, cfi ClCHaCHr-0-C --Z 0Example 21 C v A mixture of 60 g. of ethylene chlorohydrin, 5

The cyelopentadiene-satrole adduct used above is 75 g. or BF:.O(C4H0)2,and 91 g. of cyclopentadienemula:

showman. and

ethylene chlorohy indene adduct heated yielded 102 g. of the ethylenehydroxycyclopentanoindsne as acolorless oil boiling at 155-157 0.11 mm.having the at 95 G. fiorfive hours I Ezemi le 22 l hol, and 55 g. oicyclcpentadiene-in-=.

dene adduct was at 95 C. Eor seven and one-quarter hours wd worked up asabove. The benwl ether of endmthylene-hydroxycy clopentanoindanedistilled over at 1909-2 011 mm. as a colorless oil, in a'yieldamounting to as a... having the probable formula Eeanwle 23 A mixture of51 a. of tetrahydro-iuriuryl alcohol, 6 g. of BFa.O(CrHs)a, and 55 g. ofcyclopens tadiene-indene adduct was heated sixand onequarter hours at90-95 C. and yielded thetetralwdro-i'uriuryl ether ofendoethylene-hydroiwcyclopentanoindane as a colorless oil boiling atMir-173 C./0.5 mm. having the probable toron on era-om o{l ono cn l lrr-c 0- n- 1/ or cr. c Example 24' A mixture of 50 g. of cyclohexahol, 7g. of

indene adduct heated seven hours at 95 0. yielded the cyclohexyl etheror endoethylene-hydroxycyclopentanoindane a a colorless oil boiling at169-166 was mm.

' Emmple 25 8. of BF:.O(C:H53I, 48.6 of

nd 2 s. or cyclopentadiene adduct oi.- 2,4,5-trichlcrophe'nyl allylether c-chloroethyl ether of endol "are g. of memoirs; s4 3. or

55 s. of cyclopentadiene-.

was stirred for six hours at 95 was washed'with dilute sodium withwater, dried, and 88g. of a colorless oil I mm.

1 a. OlQHaCHr-O-e I The products cides, and I claim:

1. As a new compound, an acid-catalyzed adlditiomrearrangement styrene,said product ethylene-substituted p 2. As a new compound, anacid-catalyzed addition-rearrangernent chloro alcohol and an withstyrene, said pro ether of pentanol 4. As, a new ethanol 5. A methodfor. 01 endoethylene prises reacting in densinz agent adduct ofcyclopentadi having the, probable formula ski-toast l obtained accordingto vention are of potential value as intermediates for the preparationof resins, plasticizers, insectipharmaceuticals.

alcohol and an adduct' endoethylene-substituted phenyl cyclosaid productbeing a 'y-choro-p-hydroxyendoethylene-substltuted phenyl distilled invacuo to yiel boiling at 210-213 c. 0.

this inproduct of an aliphatic oi cyclopentadiene with being an ether ofendohenyl cyclopentanoi.

product of an aliphatic adduct of cyclopentadiene duct being a chloroalkyl p-chloroeth'oxyene and styrene.

mum A. mason,

